CN109594139A - A kind of purposes of polyolefin filamentary material with quick-acting antibacterial functions master batches and preparation method thereof with it - Google Patents
A kind of purposes of polyolefin filamentary material with quick-acting antibacterial functions master batches and preparation method thereof with it Download PDFInfo
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- CN109594139A CN109594139A CN201811576636.5A CN201811576636A CN109594139A CN 109594139 A CN109594139 A CN 109594139A CN 201811576636 A CN201811576636 A CN 201811576636A CN 109594139 A CN109594139 A CN 109594139A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
Abstract
A kind of purposes the present invention relates to polyolefin filamentary material with quick-acting antibacterial functions master batches and preparation method thereof with it.This method is granulated after taking nano silver inorganic antimicrobial master batch described in patent No. ZL201310571129.3, guanidine salt polymer, polyolefin carrier resin, stabilizer and dispersant by twin-screw melting extrusion, and quick-acting antibacterial functions master batches are made.Quick-acting antibacterial functions master batches prepared by the present invention wire drawing or spinning properties in polyolefin filiform material processing are good, and draping period and the period for replacing filament spinning component are compared with other similar antibacterial matrices, and the period is long.Antibacterial polyolefin filamentary material made from the method for the present invention is because containing nano silver and guanidine salt polymer binary composite synergistic antibacterial components, therefore the quick-acting performances of antibacterial are high, and it is good to wash endurance quality, whiteness is good, be suitable for production and processing disposable medical amenities non-woven cloth, bathing with bath ball the antibacterial products such as bathing towel, artificial lawn filament, carpet.
Description
Technical field
The present invention relates to anti-biotic material technical fields.More particularly it relates to a kind of polyolefin filamentary material speed
Antibacterial functions master batch is imitated, the preparation method of the quick-acting antibacterial functions master batches is further related to, it is female to further relate to the quick-acting antibacterial functions
The purposes of grain.
Background technique
Anti-biotic material has antibacterial and sterilizing function new material as a kind of, is answered in people's daily life
With, it can be very good to establish one of green screen, better people's living environment, reduction disease.It is knitted as disposable medical amenities is non-
Make cloth, it is disposable it is antifouling take non-woven cloth, agricultural fabric, furniture cloth, the lining of shoe industry, bathing bath ball bathing towel, artificial
The materials such as lawn silk, carpet pass through the one or more of specific antibacterial agents of addition, so that it may antibacterial be made and produce during the manufacturing
Product.Instantly for antibacterial agent used in market mainly based on inorganic antiseptic, inorganic antiseptic is usually to load silver, copper, zinc
The carrier compounds such as zeolite, phosphate, soluble glass, the hydroxyapatite of equal metal ions, metal ion antimicrobial component because
Its carrier is mesoporous or interlaminar action and has slow release effect, shows excellent antimicrobial long-acting.But above-described load
Type silver antibacterial agent usually 1-10 μm, is added to technique control in polyolefin filamentary material because its particle size controls in the micron-scale
Difficulty processed is larger, and wire drawing is difficult, and antibacterial filiform product is prepared in test generally by antibacterial fiber product absorption process
Or concussion method carries out, because polyolefin filiform product water imbibition is poor, especially thicker filiform water imbibition is worse, causes wherein to resist
Bacterium ingredient and test strain cannot come into full contact with, and material antibacterial effect is difficult to effectively play, and antibiotic rate is difficult to up to standard.Especially
It is, in actual use for disposable sanitary articles, time of contact section (general to require in contact 20min), antibacterial effect
Fruit require it is quick-acting, and the performance of general inorganic Ag-carried antibacterial ingredient antibacterial effect mentioned above need to contact 4h or more can.For
It achieves the goal, researcher achieves the goal often through the high organic antibacterial agent of germicidal efficiency is added, but quaternary ammonium salts, season
There are poor heat resistances for the organic antibacterial agents such as phosphonium salt class, imidazoles, pyridines, organic metal class, are easily precipitated, and low wait of safety lacks
Point, it is applicable seldom.In recent years, a kind of guanidine salt polymer class (polyguanidine) antibacterial agent, since its antibacterial high efficiency, antibacterial are wide
Spectrality, the advantages that highly-safe, stability is good, the feature of environmental protection, high heat resistance become a kind of very promising plastics antibacterial and add
Add agent.For example, document Synthesis and antimicrobial activity ofpolymeric guanidine
Andbiguanidine salts, Polymer40 (1999) 6189-6198 reports polyhexamethylene (double) guanidine hydrochloride
With polyhexamethylene (double) guanidine stearate 280 DEG C at a temperature of, still there is good sterilization to various bacteria and fungi
Effect, therefore can be used for the antimicrobial treatment of the thermoplastic polymers such as polypropylene, nylon.
Patent CN1569923A, CN1445270A and US 7282538B2, which are described, a kind of to be first made guanidine salt polymer
Antibacterial matrices, then with the processing method that it prepares antibiotic plastic, single guanidine salt polymer component precipitation is very fast, is not able to satisfy
The high product properties requirement of drinking water related product antibacterial life requirement.
Patent CN1282698C describes a kind of preparation method of polyolefin functional agglomerate, passes through graft process for guanidine salt
Polymers compositions is added in polyolefine material, and technique controlling difficulty is big, and product stability is poor.
Patent CN101724284B describes a kind of anti-bacterial thermoplastic composite and preparation method thereof, composite antibacterial
Component includes micro-nano inorganic or organic filler and guanidine salt polymer, and the composite antibacterial agent aid complicated composition, system can
Meet plastic processing requirement, but filiform processing is unable to satisfy.
Patent CN102644162B describes a kind of preparation side of antibacterial non-woven based on nano silver simple substance antibacterial agent
Method, the antibacterial matrices containing nano silver that this method is prepared into are good in non-woven cloth process industrial art performance, and antibacterial effect is excellent, health
Property safety it is high, but in application practice find preparation process in 80-100nm nano silver simple substance powder control require compared with
Height, properties of product stability are bad.
Currently, needing stable poly- of a kind of simple production process, high production efficiency, energy conservation and environmental protection, performance always in the market
The preparation method of the quick-acting antibacterial functions agglomerate materials of alkene filamentary material, and the quick-acting antibacterial functions master batches are in polyolefin filaments
In shape material processing, it is desirable that wire drawing is smooth, not network blocking, and antibacterial polyolefin filamentary material antibacterial activity height, water is made
It is high to wash superior in durability, wholesomeness.For this purpose, the present inventor completes the present invention by a large number of experiments finally.
Summary of the invention
Technical problems to be solved]
The object of the present invention is to provide a kind of polyolefin filamentary material preparation methods of quick-acting antibacterial functions master batches.
It is a further object to provide the preparation methods of the quick-acting antibacterial functions master batches.
It is a further object to provide the purposes of the quick-acting antibacterial functions master batches.
Technical solution]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of quick-acting antibacterial functions master batches of polyolefin filamentary material, it is characterised in that the quick-acting antibacterials
The nano silver particles content of functional agglomerate is 400-1400ppm, and the partial size of the nano silver particles is 5-100nm；The speed
The guanidine salt polymer content for imitating antibacterial functions master batch is weight ratio 1-10%.
The present invention also relates to a kind of preparation method of quick-acting antibacterial functions master batches of polyolefin filamentary material.This method step is such as
Under:
(1) nano silver inorganic antimicrobial master batch is prepared
Take nano silver inorganic antimicrobial master batch described in patent No. ZL201310571129.3.
(2) quick-acting antibacterial functions master batches are prepared
In parts by weight, following components are weighed:
67.5-13 parts of polyolefin carrier resin
30-70 parts of nano silver inorganic antimicrobial master batch
1-10 parts of guanidine salt polymer
0.5-2 parts of stabilizer
1-5 parts of dispersing agent
The stabilizer is silicon dioxide ultrafine powder end；
The dispersing agent is a kind of ionomer；
The nano silver inorganic antimicrobial master batch, polyolefin resin, guanidine salt polymer, stabilizer, dispersing agent is taken to add together first
Enter and stir at low speed 2-4min in high-speed mixer, then high-speed stirred 3-5min is added twin-screw extrude, melting extrusion is made
Grain, is prepared the quick-acting antibacterial functions master batches of polyolefin.
A preferred embodiment of the invention, the polyolefin carrier resin be polyethylene, polyvinyl chloride or
Polypropylene.
According to another preferred method of implementation of the present invention, the guanidine salt polymer is polyhexamethylene list guanidine salt acid
One of salt, hexamethylene, polyhexamethylene list guanidine phosphate or poly hexamethylene biguanide phosphate；
According to another preferred method of implementation of the present invention, the silicon dioxide ultrafine powder end is precipitated silica, gas phase
One of silica or superfine silicon dioxide gel.
According to another preferred method of implementation of the present invention, the ionomer is a kind of band Na+、Ca2+、
Mg2+Or Zn2+One acrylic copolymer of ethylene of metal ion, the Bu Luoke Field viscosity at 90 DEG C of the copolymer 1 are
4000-7000cps。
According to another preferred method of implementation of the present invention, the screw speed of the double screw extruder is 200-
350rpm, the double screw extruder are furnished with strength Devolatilization device.
Principle is based on the present invention: nano silver and guanidine salt polymer all have very high sterilization/bacteriostatic activity, lead to
It crosses plastic molten melt extrusion process to be combined to the two together, achievees the purpose that synergistic antimicrobial；And stabilizer silica ultrafine
The porous structure of powder has very strong adhewsive action to nano silver and guanidine salt polymer, it is delayed quickly to be precipitated, and improves sterilization/suppression
Bacterium timeliness；In addition the special guanidine radicals structure (NH) of guanidine salt polymer2C (=NH) has stabilization to nano silver, keeps it not variable
Color yellowing；The present invention uses nano silver and guanidine salt polymer compounding ingredients, and antibacterial activity is high, adds in polyolefin filamentary material
Ratio is few, is uniformly dispersed, it is ensured that not fracture of wire, not network blocking when polyolefin wire drawing；And the method for the present invention simple production process,
It is high-efficient, production cost is low, be suitble to produce the high polyolefin function of quick-acting antibacterials, white color, water-fast endurance quality in enormous quantities female
Grain.
The present invention is described in more detail below.
The present invention relates to a kind of quick-acting antibacterial functions master batches of polyolefin filamentary material, it is characterised in that the antibacterial functions
The nano silver particles content of master batch is 400-1400ppm, and the partial size of the nano silver particles is 5-100nm, the antibacterial function
The guanidine salt polymer content of energy master batch is weight ratio 1-10%.
It is known that it is nanoscale metallic silver simple substance that nano silver (Nano Silver), which is partial size,.Research finds nano silver
It is fungicide more stronger than antibiotic, can directly kills 650 various bacterias rapidly, it is made to lose fertility；Nano silver has
Permeability is strong, can promote wound healing, cell growth and damaged cell reparation；Antibacterial is lasting, safe and non-toxic, to skin also without
Any stimulate the reaction；The features such as having no drug resistance.
Guanidine salt polymer as a kind of environment-friendly type macromolecule polymer, structure kind obtain hydrophilic group part contain it is strong just
Electrically, absorption is usually in that electronegative all kinds of bacteriums, virus inhibit the synthesis of film lactones plastid, thallus caused to wither into cell membrane
It dies, reaches optimal bactericidal effect；With broad-spectrum；Effective concentration is low；Work fast；Property is stablized；Long-term antibacterial, nothing
Side effect；It is non-corrosive；It is colourless, odorless；It is nontoxic；It is non-ignitable, not quick-fried, using safe；It is moderate；Convenient transportation.
A preferred embodiment of the invention, the polyolefine material are polyethylene, polyvinyl chloride or poly- third
Alkene
The present invention also relates to a kind of preparation method of quick-acting antibacterial functions master batches of polyolefin filamentary material.The method steps are as follows:
(1) nano silver inorganic antimicrobial master batch is prepared
Take nano silver inorganic antimicrobial master batch described in patent No. ZL201310571129.3.
In this step, the silver particles content of nano silver inorganic antimicrobial master batch described in patent No. ZL201310571129.3
Containing 600-2000ppm, the silver particles partial size is 5-100nm.
Above patent describe the preparation methods of the nano silver inorganic antimicrobial master batch, and steps are as follows:
A: 1-5 parts by weight silver salt and 95-99 parts by weight are contained activity hydroxy or ketone group easy volatile solvent is added to reflux dress
In the reaction kettle set, it is stirred 60-180min at 35-60 DEG C of temperature, the silver salt is made to be completely dissolved in the solvent
In, obtain a kind of solution of homogeneous transparent；
B: homogeneous transparent solution, the 93-100 parts by weight high transparency polyolefin carrier resin, 1- that 5-20 parts by weight step A is obtained
5 weight account polyethylene pyrrolidones or polyethylene glycol and the ground molecular weight ionomer of 0.5-2 parts by weight are added to be put into and have together
In the high-speed mixer of heating and solvent reclaimer, mixed at high speed stir process 30- is carried out under conditions of 60-80 DEG C of temperature
60min, while baking removes, recycles 90% or so excess of solvent；
C: the twin-screw that step B is sufficiently mixed to the double screw extruder that the material addition draw ratio handled well is 40:1 to 64:1 squeezes
Out in machine, under conditions of processing temperature is 150-240 DEG C, being granulated by melting extrusion to get silver particles content is 600-
2000ppm, the nano silver inorganic antimicrobial master batch that nano silver particles partial size is 5-100nm；
In above-mentioned patent, the silver salt is silver nitrate, silver acetate, silver citrate or silver tartrate.
In above-mentioned patent, it is described it is described containing activity hydroxy or ketone group easy volatile solvent be methanol, ethyl alcohol or acetone.
In above-mentioned patent, the polyvinylpyrrolidone is the polyvinylpyrrolidone of 45000-130000
Ketone；
In above-mentioned patent, the polyethylene glycol is the polyethylene glycol that molecular weight is 200-4000.
In above-mentioned patent, the polyene vector resin be polyethylene, polyvinyl chloride or polypropylene,.
(2) quick-acting antibacterial functions master batches are prepared
In parts by weight, following components are weighed:
67.5-13 parts of polyolefin carrier resin
30-70 parts of nano silver inorganic antimicrobial master batch
1-10 parts of guanidine salt polymer
0.5-2 parts of stabilizer
1-5 parts of dispersing agent
The stabilizer is silicon dioxide ultrafine powder end；
The dispersing agent is a kind of ionomer.
The nano silver inorganic antimicrobial master batch, polyolefin carrier resin, guanidine salt polymer, stabilizer, dispersion are taken first
Agent is added in high-speed mixer stirs at low speed 2-4min together, then high-speed stirred 3-5min is added twin-screw extrude, and melts
Melt extruding pelletization, the quick-acting antibacterial functions master batches of polyolefin are prepared.
A preferred embodiment of the invention, the polyolefin carrier resin be polyethylene, polyvinyl chloride or
Polypropylene is marketable material.
According to another preferred method of implementation of the present invention, the guanidine salt polymer is polyhexamethylene list guanidine salt acid
One of salt, hexamethylene, polyhexamethylene list guanidine phosphate or poly hexamethylene biguanide phosphate,
For marketable material.
According to another preferred method of implementation of the present invention, the silicon dioxide ultrafine powder end be precipitated silica,
One of fumed silica or superfine silicon dioxide gel.
Silica is commonly called as white carbon black, is porous material, and composition can use SiO2·nH2O indicates, wherein nH2O be with
The form of surface hydroxyl exists.Caustic alkali and hydrofluoric acid, not soluble in water, solvent and acid can be dissolved in (except hydrofluoric acid).High temperature resistant,
It is non-ignitable, tasteless, odorless, have good electrical insulating property, water imbibition, porosity；Internal surface area is big, has good reinforcement and increasing
Viscous effect, good dispersion, suspension, vibration liquid habit.It is mainly used for rubber as a kind of environmental protection, the auxiliary agent haveing excellent performance
Glue product (including high-temperature silicon disulfide rubber), weaving, papermaking, pesticide, food additives field.
Wherein the silicon dioxide ultrafine powder end is commercially available conventional products, and purity requirement is up to 98% or more, specific surface
Product requires to be 100 ~ 1000m2/g.Silica used in the present invention is the prosperous safe micro-nano chemical industry of new peace Chemical Group or Shandong Province Shouguang
The product of factory's production and sales.
According to another preferred method of implementation of the present invention, the ionomer is some low molecular weights from poly-
Object, is a kind of polymer containing several ionic groups with polymer chain, and backbone monomers are alkene (ethylene, butadiene
Deng), ionic group is carboxyl (COO-) and sulfonic group (S03-), it is one acrylic acid copolymer of ethylene by low relative molecular mass
What object was prepared by neutralizing, institute's band metal ion is Na+、Ca2+、Mg2+Or Zn2+.Low molecular weight used in the present invention is from poly-
Object is that the trades mark such as AClyn201A, 246A, 272A, 295A or 291A of the production of U.S. Honeywell (Honeywell) company produce
Product, the Bu Luoke Field viscosity at 90 DEG C of the copolymer 1 are 4000-7000cps.
According to another preferred method of implementation of the present invention, the double screw extruder belongs to high length-diameter ratio type, and
It and must be common parallel dual-screw extruding machine or deliming type special twin screw extruder with strength Devolatilization device.The present invention
Parallel dual-screw extruding machine used is the TE-65 type machine or Nanjing Li Xuan machinery of Nanjing Da Lite extrusion machinery Co., Ltd production
The large capacity devolatilization type double screw extruder of equipment Co., Ltd production.
According to another preferred embodiment that this law is bright, the screw speed is 200-350rpm.Preferably, selected
Screw speed be 250-300rpm.Screw speed can guarantee residence time of the material in screw rod, but meeting lower than 200rpm
Influence production efficiency；And after screw speed is higher than 350rpm, material, which generates Strong shear in screw rod, can destroy nano-Ag particles and guanidine
The structure of salt polymer, influences antibacterial activity.
According to another preferred embodiment that this law is bright, the processing temperature of the screw extruder is 150-240 DEG C.
When at a temperature below 150 DEG C, it is evenly dispersed to be unfavorable for guanidine salt polymer；And when temperature is higher than 240 DEG C, it be easy to cause guanidine salt
Polymer decomposes.
According to another preferred embodiment that this law is bright, the double screw extruder is furnished with strength Devolatilization device,
Purpose is to be extracted away a small amount of poisonous and hazardous gas generated in high-temperature heating melting process in time by the device, is received
Collect in dedicated waste gas recovery storage tank, keeps gained antibacterial matrices use safer.
The quick-acting antibacterial functions obtained the invention further relates to the quick-acting antibacterial functions master batches or according to the method for the present invention
The purposes of master batch is mainly applied in polyolefin filamentous product by extruder melting extrusion wire drawing or spinning technique, such as
Disposable medical amenities non-woven cloth, the disposable antifouling lining for taking non-woven cloth, agricultural fabric, furniture cloth, shoe industry
In, bathing with bath ball bathing towel, artificial lawn filament, carpet etc..
The quick-acting antibacterial functions obtained the invention further relates to the quick-acting antibacterial functions master batches or according to the method for the present invention
Master batch is applied in polyolefin filamentary material, and nano silver particles content therein is 15-100ppm, and guanidine salt polymer content is
Weight ratio 0.04-0.5%, and wherein nano-Ag particles and guanidine salt polymer composite antibacterial component and Escherichia coli, golden yellow grape
Coccus and Candida albicans contact 1min, and antibiotic rate is i.e. up to 99% or more, and gained antibacterial polyolefin filamentous product antibacterial is durable
It has excellent performance, there is technical data to show that its effective antibacterial time is even more than 10 years.
The following detailed description of the performance detection test of quick-acting antibacterial functions master batches prepared by the present invention.
Detection method is as follows with testing result.
A, the wire drawing of the present invention quick-acting antibacterial functions master batches application squeezes out evaluation test and (is with polyolefin PE bath ball material
Example):
It is melted after the quick-acting antibacterial functions master batches of PE base of the invention are uniformly mixed with polyolefin PE resin by a certain percentage through screw rod
Melt extrusion wire drawing to be made compared with crin, the nano silver particles content in made PE wire material is 40ppm, and guanidine salt polymer content is
Weight ratio 0.3%, and PE string diameters of gained antibacterial are 0.2mm.It chooses and silver-colored superfines antibacterial is carried by conventional antimicrobial component basic zirconium phosphate
The PE antibacterial matrices that agent is prepared into carry out wire drawing comparative evaluation experiment, while being also prepared for not adding nano silver inorganic antimicrobial ingredient
And antibacterial PE of the single antibacterial agent of 0.3% guanidine salt polymer are only added, it is spare as other control sample.
Processing experiment shows to be added to when producing the PE silk of same specification (string diameter 0.2mm) quick-acting obtained by the present invention
The PE wire drawing period of antibacterial matrices is long: the draping period --- and >=1/48 hours；Change element period --- >=45 days；And add
Add the wire drawing period of silver-zirconium phosphate antimicrobial are as follows: the draping period --- >=1/12 hours；Change element period ---
>=20 days.
B, the anti-microbial property evaluation test of the present invention quick-acting antibacterial functions master batches application (is with polyolefin PE bath ball material
Example):
To antibacterial PE obtained in the above A, according to standard GB15979-2002 " Disposable Sanitary Accessory standard appendix C
Concussion method " it is tested, the results showed that the antibacterial silk and Escherichia coli (ATCC25922), staphylococcus aureus
(ATCC6538) and Candida albicans (ATCC10231) contact action 1min, antibiotic rate are up to 99% or more.
C, the antibacterial endurance quality evaluation test of the quick-acting antibacterial functions master batch applications of the present invention is (with polyolefin PE bath ball material
For):
To antibacterial PE obtained in the above A, according to standard FZ/73023-2006, " antibiosis knitting product appendix C antibiotic fabric is tried
Sample decantation test method " tested, the results showed that the antibacterial PE after water washing 100 times, to Escherichia coli
(ATCC25922), staphylococcus aureus (ATCC6538) and Candida albicans (ATCC10231) antibiotic rate are still up to 90% or more；
While washing test experiments discovery, antibacterial silk before washing are carried out to single guanidine salt polymeric component antibacterial PE is only added in the above A
Still to Escherichia coli (ATCC25922), staphylococcus aureus (ATCC6538) and Candida albicans (ATCC10231) antibiotic rate
Up to 99% or more, after being washed 100 times using same method, to Escherichia coli (ATCC25922), staphylococcus aureus
(ATCC6538) and Candida albicans (ATCC10231) antibiotic rate is respectively 50%, 30%, 28%, and antibiotic rate reduces very much, because
Guanidine salt polymer good water solubility, the antibacterial silk made of its one-component are precipitated comparatively fast in water, and washing durability is poor.This comparison
Experiment further illustrates that recipe ingredient collocation washing endurance quality is more excellent in the antibacterial functions master batch of the method for the present invention preparation.
D, the quick-acting antibacterial functions master batch application gained antibacterial silk material whiteness evaluation tests of the present invention are (with polyolefin PE bath ball material
For material):
To antibacterial PE obtained in the above A, according to standard GB/T17644-2008 " textile fabric whiteness colorimetric assay method "
It is tested, the results showed that antibacterial PE whiteness W is 76.5760%, and is not added with antimicrobial component and blank PE whiteness is made
77.4870% compares, and differs very little.
Nano-sized silver constituent of the present invention is derived from patent ZL201310571129.3, describes the nano-Ag particles in this patent
Partial size 5-100nm, distribution is relatively uniform and highly-safe, and anti-microbial property is good, and stability is splendid；Antibacterial of the present invention is female simultaneously
The guanidine salt polymer microbiocidal composition that environment-friendly high-efficiency is increased in grain preparation process, further increases material antibacterial activity, reaches
Quick-acting purposes.It is tested by above-mentioned test evaluation, test result is it also clearly appears that quick-acting antibacterial functions prepared by the present invention are female
The antibacterial activity of grain is very high, and being divided into nano silver particles content in composite antibacterial group is 15-100ppm and guanidine salt polymer content
Under the conditions of being weight ratio 0.1-0.5%, obtained antibacterial polyolefin filamentary material and with Escherichia coli (ATCC25922), golden yellow
Color staphylococcus (ATCC6538) and Candida albicans (ATCC10231) contact action 1min, antibiotic rate i.e. up to 99% or more, and
And after water washing 100 times, antibiotic rate is still up to 90% or more.The quick-acting antibacterial functions master batches of present invention gained are in polyolefin simultaneously
Strong applicability in wire drawing or spinning process, process-cycle are long.In addition, the quick-acting antibacterial functions master batches obtained by the present invention are made
Antibacterial polyolefin filamentary material whiteness is good, meets high-quality antimicrobial product technical requirements.
[beneficial effect]
The present invention have it is following the utility model has the advantages that
Few using equipment, simple process is environmentally friendly, is convenient for large-scale industrial production；Quick-acting antibacterials prepared by the present invention
Functional agglomerate is safe to use, and antibacterial is efficiently quick-acting, especially suitable for the relatively crin shape polyolefine material product of water imbibition difference,
The polyolefin PE bath ball silk and Escherichia coli, staphylococcus aureus and Candida albicans for being such as added to antibacterial matrices of the present invention connect
Touching acts on 1min, and antibiotic rate washes superior in durability i.e. up to 99% or more；The life of the quick-acting antibacterial functions master batches of the present invention
Produce it is at low cost, have the very strong market competitiveness.
[specific embodiment]
The present invention is better understood with by these following embodiments.
Embodiment 1
(1) nano silver inorganic antimicrobial master batch is prepared
The record of embodiment 2 in patent No. ZL201310571129.3 specification is taken, silver particles content is made and contains 1200ppmLDPE
Base nano silver inorganic antimicrobial antibacterial matrices.
(2) quick-acting antibacterial functions master batches are prepared
In parts by weight, following components are weighed:
59.5 parts of LDPE vector resin
33.5 parts of nano silver inorganic antimicrobial master batch
3 parts of polyhexamethylene list guanidine hydrochloride
1 part of fumed silica
3 parts of 201A ionomer
The nano silver inorganic antimicrobial master batch, LDPE vector resin, polyhexamethylene list guanidine hydrochloride, vapor phase method two are taken first
Silica, 201A ionomer are added in high-speed mixer stir at low speed 2min together, high-speed stirred 4min, and double spiral shells are then added
In bar extruder, melting extrusion is granulated under 150-170 DEG C of processing temperature and 250rpm revolving speed, and silver particles content, which is prepared, is
400ppm, polyhexamethylene list guanidine hydrochloride content be weight percentage 3% the quick-acting antibacterial functions master batches of PE.
Embodiment 2
(1) nano silver inorganic antimicrobial master batch is prepared
The record of embodiment 2 in patent No. ZL201310571129.3 specification is taken, silver particles content is made and contains 1200ppmLDPE
Base nano silver inorganic antimicrobial antibacterial matrices.
(2) quick-acting antibacterial functions master batches are prepared
In parts by weight, following components are weighed:
22 parts of LLDPE polyethylene carrier resin
67 parts of nano silver inorganic antimicrobial master batch
5 parts of hexamethylene
2 parts of precipitated silica
4 parts of 291A ionomer
The nano silver inorganic antimicrobial master batch, LLDPE vector resin, hexamethylene, the precipitation method are taken first
Silica, 291A ionomer are added in high-speed mixer stir at low speed 4min together, high-speed stirred 5min, are then added double
In screw extruder, melting extrusion is granulated under 150-170 DEG C of processing temperature and 250rpm revolving speed, and silver particles content is prepared
It is weight percentage the 5% quick-acting antibacterial functions master batches of LLDPE for 800ppm, hexamethylene content.
Embodiment 3
(1) nano silver inorganic antimicrobial master batch is prepared
The record of embodiment 3 in patent No. ZL201310571129.3 specification is taken, silver particles content base containing 1800ppmPP is made
Nano silver inorganic antimicrobial antibacterial matrices.
(2) quick-acting antibacterial functions master batches are prepared
In parts by weight, following components are weighed:
52.5 parts of PP polypropylene carrier resin
40 parts of nano silver inorganic antimicrobial master batch
5 parts of poly hexamethylene biguanide phosphate
0.5 part of superfine silicon dioxide gel
2 parts of 201A ionomer
The nano silver inorganic antimicrobial master batch, PP polypropylene carrier resin, poly hexamethylene biguanide phosphate, ultra-fine is taken first
Silica dioxide gel, 201A ionomer are added in high-speed mixer stir at low speed 2min together, high-speed stirred 4min, then plus
Enter in double screw extruder, melting extrusion is granulated under 190-220 DEG C of processing temperature and 300rpm revolving speed, and silver particles are prepared
Content be 720ppm, poly hexamethylene biguanide phosphate content be weight percentage 5% the quick-acting antibacterial functions master batches of PP.
Embodiment 4
(1) nano silver inorganic antimicrobial master batch is prepared
The record of embodiment 3 in patent No. ZL201310571129.3 specification is taken, silver particles content base containing 1800ppmPP is made
Nano silver inorganic antimicrobial antibacterial matrices.
(2) quick-acting antibacterial functions master batches are prepared
In parts by weight, following components are weighed:
16 parts of PP polypropylene carrier resin
70 parts of nano silver inorganic antimicrobial master batch
8 parts of phosphate of polyhexamethylene list guanidine
2 parts of fumed silica
4 parts of 201A ionomer
The nano silver inorganic antimicrobial master batch, PP polypropylene carrier resin, polyhexamethylene list guanidine phosphate, gas phase are taken first
Method silica, 201A ionomer are added in high-speed mixer stir at low speed 4min together, then high-speed stirred 5min is added
In double screw extruder, melting extrusion is granulated under 190-220 DEG C of processing temperature and 300rpm revolving speed, and silver particles are prepared and contain
Amount be 1260ppm, polyhexamethylene list guanidine phosphate content be weight percentage 8% the quick-acting antibacterial functions master batches of PP
Embodiment 5
(1) nano silver inorganic antimicrobial master batch is prepared
The record of embodiment 4 in patent No. ZL201310571129.3 specification is taken, silver particles content is made and contains 1500ppmPVC
Base nano silver inorganic antimicrobial antibacterial matrices.
(2) quick-acting antibacterial functions master batches are prepared
In parts by weight, following components are weighed:
42 parts of PVC polyvinyl chloride vector resin
50 parts of nano silver inorganic antimicrobial master batch
4 parts of hexamethylene
1 part of fumed silica
3 parts of 246A ionomer
The nano silver inorganic antimicrobial master batch, PVC polyvinyl chloride vector resin, poly hexamethylene biguanide hydrochlorate, gas are taken first
Phase method silica, 246A ionomer are added in high-speed mixer stir at low speed 2min together, high-speed stirred 4min, then plus
Enter in double screw extruder, melting extrusion is granulated under 160-190 DEG C of processing temperature and 250rpm revolving speed, and silver particles are prepared
Content be 750ppm, hexamethylene content be weight percentage 4% the quick-acting antibacterial functions master batches of PVC.
Using test method described in this specification, the polyolefin filamentary material for testing the present embodiment 1-5 preparation is used
The performance of quick-acting antibacterial functions master batches, test result are listed in Table 1 below.
Claims (15)
1. a kind of polyolefin filamentary material preparation method of quick-acting antibacterial functions master batches, it is characterised in that the step of this method such as
Under:
(1) nano silver inorganic antimicrobial master batch is prepared, steps are as follows:
A: 1-5 parts by weight silver salt and 95-99 parts by weight are contained activity hydroxy or ketone group easy volatile solvent is added to reflux dress
In the reaction kettle set, it is stirred 60-180min at 35-60 DEG C of temperature, the silver salt is made to be completely dissolved in the solvent
In, obtain a kind of solution of homogeneous transparent；The silver salt is silver nitrate, silver acetate, silver citrate or silver tartrate, described to contain
Activity hydroxy or ketone group easy volatile solvent are methanol, ethyl alcohol or acetone；
B: homogeneous transparent solution, the 93-100 parts by weight high transparency polyolefin carrier resin, 1- that 5-20 parts by weight step A is obtained
5 weight account polyethylene pyrrolidones or polyethylene glycol and the ground molecular weight ionomer of 0.5-2 parts by weight are added to be put into and have together
In the high-speed mixer of heating and solvent reclaimer, mixed at high speed stir process 30- is carried out under conditions of 60-80 DEG C of temperature
60min, while baking removes, recycles 90% or so excess of solvent；The polyvinylpyrrolidone is the poly- second of 45000-130000
Vinyl pyrrolidone, the polyethylene glycol are the polyethylene glycol that molecular weight is 200-4000；
C: the twin-screw that step B is sufficiently mixed to the double screw extruder that the material addition draw ratio handled well is 40:1 to 64:1 squeezes
Out in machine, under conditions of processing temperature is 150-240 DEG C, being granulated by melting extrusion to get silver particles content is 600-
2000ppm, the nano silver inorganic antimicrobial master batch that nano silver particles partial size is 5-100nm；
(2) quick-acting antibacterial functions master batches are prepared
In parts by weight, following components are weighed:
67.5-13 parts of polyolefin carrier resin
30-70 parts of nano silver inorganic antimicrobial master batch
1-10 parts of guanidine salt polymer
0.5-2 parts of stabilizer
1-5 parts of dispersing agent
The stabilizer is silicon dioxide ultrafine powder end；
The dispersing agent is a kind of ionomer；
The nano silver inorganic antimicrobial master batch, polyolefin carrier resin, guanidine salt polymer, stabilizer, dispersing agent one are taken first
It rises in addition high-speed mixer and stirs at low speed 2-4min, then high-speed stirred 3-5min is added twin-screw extrude, processing
Temperature is under conditions of 150-240 DEG C, and melting extrusion is granulated, and polyolefin filamentary material is prepared with quick-acting antibacterial functions mothers
Grain.
2. preparation method according to claim 1, it is characterised in that the polyolefin carrier resin is polyethylene, polychlorostyrene
Ethylene or polypropylene.
3. preparation method according to claim 1, it is characterised in that the guanidine salt polymer is polyhexamethylene list guanidine
One in hydrochloride, hexamethylene, polyhexamethylene list guanidine phosphate or poly hexamethylene biguanide phosphate
Kind.
4. preparation method according to claim 1, it is characterised in that the silicon dioxide ultrafine powder end is precipitating dioxy
One of SiClx, fumed silica or superfine silicon dioxide gel.
5. preparation method according to claim 1, it is characterised in that the purity of the silica is up to 98% or more, institute
The specific surface area for the silica stated is 100 ~ 500m2/g。
6. preparation method according to claim 1, it is characterised in that the ionomer is a kind of band Na+、
Ca2+、Mg2+Or Zn2+One acrylic copolymer of ethylene of metal ion, the Bu Luoke Field viscosity at 90 DEG C of the copolymer 1
For 4000-7000cps.
7. preparation method according to claim 1, it is characterised in that the screw speed of the double screw extruder is
200-350rpm, the double screw extruder are furnished with strength Devolatilization device.
8. a kind of quick-acting antibacterial functions of polyolefin filamentary material of -7 any preparation method preparations according to claim 1
Master batch.
9. the quick-acting antibacterial functions master batches of polyolefin filamentary material as claimed in claim 8, it is characterised in that described quick-acting anti-
The nano silver particles content of bacterium functional agglomerate is 400-1400ppm, and the partial size of the nano silver particles is 5-100nm.
10. the quick-acting antibacterial functions master batches of polyolefin filamentary material as claimed in claim 8, it is characterised in that described quick-acting anti-
The guanidine salt polymer content of bacterium functional agglomerate is weight ratio 1-10%.
11. a kind of polyolefin filamentary material, which is characterized in that include the quick-acting antibacterials any just like in claim 8-10
Functional agglomerate.
12. polyolefin filamentary material as claimed in claim 11, which is characterized in that nano silver particles content therein is 15-
100ppm, guanidine salt polymer content are weight ratio 0.04-0.5%.
13. the polyolefin filamentary material as described in claim 11 or 12, which is characterized in that the polyolefin base resin is
Polyethylene, polyvinyl chloride or polypropylene.
14. the polyolefin filamentary material as described in claim 11 or 12, it is characterised in that wherein nano-Ag particles and guanidine salt are poly-
Close object composite antibacterial component and Escherichia coli, staphylococcus aureus and Candida albicans contact 1min, antibiotic rate i.e. up to 99% with
On.
15. polyolefin filamentary material as claimed in claim 13, it is characterised in that wherein nano-Ag particles and guanidine salt polymer
Composite antibacterial component and Escherichia coli, staphylococcus aureus and Candida albicans contact 1min, and antibiotic rate is i.e. up to 99% or more.
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